CN101065473A - 洗涤剂组合物 - Google Patents
洗涤剂组合物 Download PDFInfo
- Publication number
- CN101065473A CN101065473A CNA2005800408382A CN200580040838A CN101065473A CN 101065473 A CN101065473 A CN 101065473A CN A2005800408382 A CNA2005800408382 A CN A2005800408382A CN 200580040838 A CN200580040838 A CN 200580040838A CN 101065473 A CN101065473 A CN 101065473A
- Authority
- CN
- China
- Prior art keywords
- detergent composition
- capsule
- preferred
- sealed
- lipase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 174
- 239000003599 detergent Substances 0.000 title claims abstract description 89
- 239000002304 perfume Substances 0.000 claims abstract description 47
- 108090001060 Lipase Proteins 0.000 claims abstract description 46
- 102000004882 Lipase Human genes 0.000 claims abstract description 46
- 239000002245 particle Substances 0.000 claims abstract description 31
- 238000009835 boiling Methods 0.000 claims abstract description 5
- 235000013599 spices Nutrition 0.000 claims description 72
- 239000002775 capsule Substances 0.000 claims description 52
- 229920002472 Starch Polymers 0.000 claims description 47
- 235000019698 starch Nutrition 0.000 claims description 46
- 239000004367 Lipase Substances 0.000 claims description 45
- 235000019421 lipase Nutrition 0.000 claims description 45
- 239000008107 starch Substances 0.000 claims description 45
- 150000002148 esters Chemical class 0.000 claims description 44
- 239000003205 fragrance Substances 0.000 claims description 43
- 238000005406 washing Methods 0.000 claims description 31
- 239000000796 flavoring agent Substances 0.000 claims description 30
- 235000019634 flavors Nutrition 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 17
- 150000001413 amino acids Chemical class 0.000 claims description 15
- 235000001014 amino acid Nutrition 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000002632 lipids Chemical class 0.000 claims description 8
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 7
- 241000223258 Thermomyces lanuginosus Species 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 4
- 229920001184 polypeptide Polymers 0.000 claims description 3
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 3
- 238000012797 qualification Methods 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- MDHYEMXUFSJLGV-UHFFFAOYSA-N phenethyl acetate Chemical compound CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003275 alpha amino acid group Chemical group 0.000 claims 1
- 238000010936 aqueous wash Methods 0.000 claims 1
- 239000000428 dust Substances 0.000 claims 1
- 238000004900 laundering Methods 0.000 abstract 1
- -1 acetate ester Chemical class 0.000 description 53
- 239000003921 oil Substances 0.000 description 45
- 239000003795 chemical substances by application Substances 0.000 description 33
- 102000004190 Enzymes Human genes 0.000 description 24
- 108090000790 Enzymes Proteins 0.000 description 24
- 229940088598 enzyme Drugs 0.000 description 24
- 150000002576 ketones Chemical class 0.000 description 21
- 150000003839 salts Chemical group 0.000 description 18
- 150000001299 aldehydes Chemical class 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 239000004744 fabric Substances 0.000 description 14
- 239000002585 base Substances 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000013543 active substance Substances 0.000 description 11
- 239000002671 adjuvant Substances 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 11
- 239000003945 anionic surfactant Substances 0.000 description 10
- 239000000975 dye Substances 0.000 description 10
- 239000004615 ingredient Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
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- 238000004140 cleaning Methods 0.000 description 7
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 7
- 150000002825 nitriles Chemical class 0.000 description 7
- 150000002978 peroxides Chemical group 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 239000007844 bleaching agent Substances 0.000 description 6
- 150000001720 carbohydrates Chemical class 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 6
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 6
- 150000004965 peroxy acids Chemical class 0.000 description 6
- 239000003352 sequestering agent Substances 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- VPKMGDRERYMTJX-CMDGGOBGSA-N 1-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-1-penten-3-one Chemical compound CCC(=O)\C=C\C1C(C)=CCCC1(C)C VPKMGDRERYMTJX-CMDGGOBGSA-N 0.000 description 5
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 5
- 241000282326 Felis catus Species 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 5
- 238000005202 decontamination Methods 0.000 description 5
- 230000003588 decontaminative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 229910021653 sulphate ion Inorganic materials 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- FINOAUDUYKVGDS-UHFFFAOYSA-N (2-tert-butylcyclohexyl) acetate Chemical compound CC(=O)OC1CCCCC1C(C)(C)C FINOAUDUYKVGDS-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- ZCTQGTTXIYCGGC-UHFFFAOYSA-N Benzyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OCC1=CC=CC=C1 ZCTQGTTXIYCGGC-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- UZFLPKAIBPNNCA-BQYQJAHWSA-N alpha-ionone Chemical compound CC(=O)\C=C\C1C(C)=CCCC1(C)C UZFLPKAIBPNNCA-BQYQJAHWSA-N 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 239000003623 enhancer Substances 0.000 description 4
- 229920000591 gum Polymers 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- HLCSDJLATUNSSI-JXMROGBWSA-N (2e)-3,7-dimethylocta-2,6-dienenitrile Chemical compound CC(C)=CCC\C(C)=C\C#N HLCSDJLATUNSSI-JXMROGBWSA-N 0.000 description 3
- KHQDWCKZXLWDNM-KPKJPENVSA-N (e)-2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)but-2-en-1-ol Chemical compound CC\C(CO)=C/CC1CC=C(C)C1(C)C KHQDWCKZXLWDNM-KPKJPENVSA-N 0.000 description 3
- LUZDYPLAQQGJEA-UHFFFAOYSA-N 2-Methoxynaphthalene Chemical compound C1=CC=CC2=CC(OC)=CC=C21 LUZDYPLAQQGJEA-UHFFFAOYSA-N 0.000 description 3
- GVONPEQEUQYVNH-SNAWJCMRSA-N 2-Methyl-3-(2-pentenyl)-2-cyclopenten-1-one Chemical compound CC\C=C\CC1=C(C)C(=O)CC1 GVONPEQEUQYVNH-SNAWJCMRSA-N 0.000 description 3
- NFAVNWJJYQAGNB-UHFFFAOYSA-N 2-methylundecanal Chemical compound CCCCCCCCCC(C)C=O NFAVNWJJYQAGNB-UHFFFAOYSA-N 0.000 description 3
- OHRBQTOZYGEWCJ-UHFFFAOYSA-N 3-(3-propan-2-ylphenyl)butanal Chemical compound CC(C)C1=CC=CC(C(C)CC=O)=C1 OHRBQTOZYGEWCJ-UHFFFAOYSA-N 0.000 description 3
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DUKPKQFHJQGTGU-UHFFFAOYSA-N Hexyl salicylic acid Chemical compound CCCCCCOC(=O)C1=CC=CC=C1O DUKPKQFHJQGTGU-UHFFFAOYSA-N 0.000 description 3
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- 239000006210 lotion Substances 0.000 description 3
- BFBPISPWJZMWJN-UHFFFAOYSA-N methyl 2-[(7-hydroxy-3,7-dimethyloctylidene)amino]benzoate Chemical compound COC(=O)C1=CC=CC=C1N=CCC(C)CCCC(C)(C)O BFBPISPWJZMWJN-UHFFFAOYSA-N 0.000 description 3
- IPWBXORAIBJDDQ-UHFFFAOYSA-N methyl 2-hexyl-3-oxocyclopentane-1-carboxylate Chemical compound CCCCCCC1C(C(=O)OC)CCC1=O IPWBXORAIBJDDQ-UHFFFAOYSA-N 0.000 description 3
- KVWWIYGFBYDJQC-UHFFFAOYSA-N methyl dihydrojasmonate Chemical compound CCCCCC1C(CC(=O)OC)CCC1=O KVWWIYGFBYDJQC-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- 239000002994 raw material Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
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- 239000002904 solvent Substances 0.000 description 3
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Classifications
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
- C11D3/502—Protected perfumes
- C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
Abstract
包含高效脂肪酶和颗粒的洗涤剂组合物，所述颗粒包含胶囊包封的香料。优选的香料在0.10MPa(760mm Hg)具有260℃或更低的沸点并且具有至少3.0的计算CLogP。胶囊包封的香料颗粒可用于洗涤组合物，以便在洗涤的所有阶段、尤其是在洗涤阶段提供有效的香料递送。
Description
技术领域
本发明涉及洗涤剂组合物，尤其是衣物洗涤剂组合物。本发明更具体地涉及包含脂肪分解酶或脂肪酶的洗涤剂。
发明背景和现有技术
自20世纪80年代晚期以来，人们一直通过在洗涤剂中使用脂肪酶来移除脂肪污垢。已知，脂肪酶对于含脂肪酶的洗涤剂组合物的香料产生影响。对用于含脂肪酶的洗涤剂组合物中的香料的选择记录于EP-A-430315，其中描述了使用香料来防止由于使用脂肪酶而产生的恶臭，所述香料包含按重量计至少25％的限定香料原料，并且包含按重量计少于50％的衍生自含有1至7个碳原子的脂肪酸的酯。
直到最近，主要的市售脂肪酶在洗涤过程中水分含量较低的干燥阶段尤其有效。然而，最近已经开发出更高效的脂肪酶，该脂肪酶在清洗过程的洗涤阶段也是有效的。此类酶的实施例如WO00/60063和Research Disclsoure IP6553D中所描述。在消费者日益期望洗涤过程的所有阶段都能散发令人愉悦香味的环境中，洗涤剂配制人员要生产令消费者满意的香味变得更加困难，其中消费者最能注意到脂肪酶对洗涤剂组合物中香料的影响是在储藏后，并且因此，在洗涤过程中。这对于用于手洗过程的洗涤剂尤其是个问题。本发明人已经发现可以减轻上述问题，甚至对于包含新的高效脂肪酶的洗涤剂制剂也是如此。此外，本发明人已经发现了可用于此类洗涤剂制剂的具体优选的香料。
本发明的定义
依照本发明，提供了一种洗涤剂组合物，所述组合物包含：
1.一种脂肪酶，该脂肪酶为具有下述氨基酸序列的多肽：a)具有与得自Humicola lanuginosa菌株DSM 4109的野生型脂肪酶至少90％的同一性；b)与所述野生型脂肪酶相比，包括在三维结构表面距E1或Q249 15埃之内一个电中性或带负电的氨基酸被一个带正电的氨基酸所取代；以及c)在C-末端包括一个附加肽段；和/或(d)在N-末端包括一个附加肽段，和/或(e)符合下列限定条件：i)在所述野生型脂肪酶的E210位含有一个带负电的氨基酸；ii)在对应于所述野生型脂肪酶90-101位的区域含有一个带负电的氨基酸；和iii)在对应于所述野生型脂肪酶的N94位含有一个中性或带负电的氨基酸和/或在对应于所述野生型脂肪酶90-101位的区域具有一个负或中性净电荷；和
2.一种胶囊包封的香料颗粒，该颗粒包括(a)包含一种或多种水溶性羟基化合物的至少部分水溶性的固体基质，优选淀粉；和(b)被固体基质所胶囊包封的香料油。
脂肪酶可以为如上文所定义，符合标准(a)、(b)和(c)和/或(e)的多肽。
在本发明的另一个实施方案中，胶囊包封的香料油包含按重量计至少1％，或至少5％重量，或按重量计甚至至少10％，或按重量计甚至至少20％、30％、40％、50％、60％、70％、80％或90％ 的至少一种香料成分，所述香料成分在0.10MPa(36KNm-2(760mmHg)具有260℃或更低的沸点并且具有至少3.0的其辛醇/水系数P的log10计算值(ClogP)。在另一个实施方案中，胶囊包封的香料油包含至少一种衍生自含有1至7个碳原子的脂肪酸的酯，通常按重量计至少1％，或至少5％重量，或按重量计甚至至少10％，或按重量计甚至至少20％、30％、40％、50％、60％、70％、80％或90％重量的酯，所有百分比均基于胶囊包封的香料颗粒中全部香料油的重量。本发明人已经发现，两种特殊的香料酯对于脂肪酶的存在尤其敏感，因此本发明在胶囊包封的香料油包含乙酸苄酯和/或乙酸苯乙酯时尤其有益。
在本发明的另一个实施方案中，提供了包含香料组合物的洗涤剂组合物，所述香料组合物包含胶囊包封在香料颗粒中的香料油和任何任选的附加香料油，所述香料组合物包含按重量计至少10％，或至少20％、30％、40％、50％、60％、70％、80％或甚至90％重量的一种或多种香料组分，所述香料组分具有大于0但小于或等于5.81E-22g(350道尔顿)的分子量，至少80％的所述一种或多种香料组分具有至少2.4的cLogP，所述香料组合物包含至少5％的具有至少2.4的cLogP的所述一种或多种香料组分。
发明详述
除非另外指明，本文所有的百分比和比率均按重量计算。除非另外指明，百分比和比率均基于总组合物计算。本文中，描述酶(例如涉及氨基酸改性、氨基酸分组和氨基酸特性)所用的命名与WO00/60063中所述的一致。
适用于本发明的脂肪酶可选自由EC号码3.1分类的能够水解酯键的酶，优选由EC号码3.1.1分类的水解羧基酯键的酶。在这种分类内，尤其优选的是由EC号码3.1.1.3分类的脂肪酶，最优选的是具有一次洗净性能的那些，如WO00/60063、WO99/42566、WO02/062973、WO97/04078、WO97/04079和US5869438中所描述。
优选的脂肪酶描述于WO00/60063。如描述于WO00/60063的适用于本发明的优选脂肪酶是参考衍生自Humicola Lanuginosa种类DSM 4109野生型脂肪酶的脂肪酶(参考脂肪酶)来描述的。参考脂肪酶也被称为Lipolase(Novozymes的注册商品名)。它被描述于EP258068和EP305216，并且具有US5869438的序列编号2的1-269位所显示的氨基酸序列。
可用于本发明的最优选一次洗净脂肪酶可以商品名LIPEX(Novozymes的注册商品名)获得，它是Humicolalanuginosa(Thermomyces lanuginosus)脂肪酶(Novozymes的Lipolase注册商品名)的变体，具有突变T231R和N233R。
掺入本发明洗涤剂组合物中的脂肪酶通常存在的量为10至20000LU/g洗涤剂组合物，或甚至100至10000LU/g。用于脂肪酶活性的LU单位定义于WO99/42566。洗涤溶液中的脂肪酶用量典型地为0.02至2mg/L酶，更典型地0.1至2mg/L作为酶蛋白质。
可以任何方便的形式，通常以不成灰粒状、稳定液体或涂敷酶颗粒的形式，将脂肪酶掺入到洗涤剂组合物中。可供选择地，浆液也可以是适合的形式。
可用于本发明的至少部分水溶性的羟基化合物优选地选自碳水化合物，所述碳水化合物可以为以下任何一种或它们的混合物：i)简单糖(或单糖)；ii)低聚糖(定义为由2至10个单糖分子组成的碳水化合物链)；iii)多糖(定义为由至少11个，或更常见地至少35个单糖分子组成的碳水化合物链)；和iv)淀粉。
既可用直链碳水化合物链也可用支链碳水化合物链。此外，可以使用化学改性的淀粉和多糖/低聚糖。典型的改性包括添加与存在于表面活性剂的那些完全相同的烷基、芳基等形式的疏水部分，以向这些化合物赋予某种表面活性。
合适胶囊包封材料的其它实施例包括诸如藻酸酯、角叉菜胶、琼脂-琼脂、果胶酸的所有天然或合成树胶；和诸如阿拉伯树胶、黄蓍胶和刺梧桐树胶的天然树胶；甲壳质和脱乙酰壳多糖；纤维素和纤维素衍生物，所述纤维素衍生物包括i)醋酸纤维素和乙酸邻苯二甲酸纤维素(CAP)；ii)羟丙基甲基纤维素(HPMC)；iii)羧甲基纤维素(CMC)；iv)所有肠溶包衣/水溶性包衣、以及它们的混合物。
尤其优选的胶囊包封基质原料包括淀粉。合适的实施例可由生淀粉、预先胶凝化的淀粉、衍生自块茎、豆类、谷类食物和谷物的改性淀粉，例如玉米淀粉、小麦淀粉、大米淀粉、蜡质种玉米淀粉、燕麦淀粉、木薯淀粉、蜡质大麦、蜡质大米淀粉、香米淀粉、预胶凝玉米淀粉、马铃薯淀粉、木薯淀粉、燕麦淀粉、木薯淀粉、以及它们的混合物制成。
适于用作本发明中胶囊包封基质的改性淀粉包括水解淀粉、酸稀释淀粉、长链烃的淀粉酯、乙酸淀粉酯、辛烯基琥珀酸淀粉酯、以及它们的混合物。
术语“水解淀粉”是指典型通过酸水解和/或酶水解淀粉而获得的低聚糖型原料，优选玉米淀粉。用于包括在本发明中的合适水解淀粉包括麦芽糖糊精和玉米糖浆固体。用于同淀粉酯的混合物一起包含的水解淀粉具有约10至约36DE的右旋糖当量(DE)值。DE值是相对于右旋糖所测得的水解淀粉还原当量，以百分比表示(以折干计算)。DE值越高，存在的还原糖就越多。用于测定DE值的方法可见于Standard Analytical Methods of the Member Companies of CornIndustries Research Foundation，第6版，Corn Refineries Association，Inc.，Washington，DC 1980年，D-52。
可以用具有在约0.01％至约10.0％范围内取代程度的淀粉酯来胶囊包封本发明的香料油。改性酯的烃部分应该为C5至C16碳链。优选地，多种类型的辛烯基琥珀酸酯(OSAN)取代的蜡质种玉米淀粉如1)蜡质淀粉：酸稀释和OSAN取代的，2)玉米糖浆固体的共混物：蜡质淀粉、OSAN取代和糊精化的，3)蜡质淀粉：OSAN取代和糊精化的，4)玉米糖浆固体的共混物或麦芽糖糊精与蜡质淀粉的共混物：酸稀释，OSAN取代，然后熬煮并且喷雾干燥，5)蜡质淀粉：酸稀释并且OSAN取代，然后熬煮并且喷雾干燥，和6)高粘度和低粘度的上述改性(基于酸处理的程度)也可用于本发明。
因为淀粉改性剂的疏水特性，具有乳化和乳液稳定能力的改性淀粉(如辛烯基琥珀酸淀粉酯)具有在乳液中夹带香料油小滴的能力。由于热力学因素(即疏水的交互作用)和乳液因为空间位阻而产生的稳定性，香料油在溶解于洗涤溶液以前都保持夹带在改性的淀粉中。在胶囊包封之前，香料可以被吸附或被吸附到载体上。载体的合适实施例如WO 97/11151中所述，或可以为聚合材料。沸石是尤其优选的载体，例如象WO97/11151中更为详细地描述。
制造本发明的淀粉胶囊包封材料的其它已知方法包括但不限于流化床附聚、挤出、冷却/结晶方法，以及使用相转移催化剂来促进界面的聚合反应。
其它合适的基质原料和方法细节公开于例如1976年7月27日公布的Brenner等人的美国专利3,971,852。
香料油
本文所用表达“香料油”旨在指香料原料或成分或它们的组合。虽然这些物质通常在标准的温度和压力条件下与水不混溶，但是少数可以与水混溶。香料油可包含一种香料成分或超过一种香料成分的混合物。除了通过胶囊包封的香料颗粒存在于本发明洗涤剂组合物中的香料油之外，附加的香料油还可以通过如下文所讨论的其它递送体系存在于洗涤剂中。存在于胶囊包封的香料油中的香料成分的总和与任何任选的附加香料油提供了洗涤剂组合物的香料组合物。
本发明人已经发现，通常脂肪酶，尤其是本发明必需的高效脂肪酶，会使贮藏时的香料稳定性出现问题，这意味着同加入洗涤剂制剂的香料量相比，消费者察觉的香料香味不仅减少了，而且也可能受到了不利影响，因此它不是由香料商所选择的香味。这个问题尤其在洗涤过程中引起消费者注意，并且本发明人已经发现，胶囊包封的香料不仅在贮藏时具有一定程度的保护，并且令人惊讶的是胶囊包封的香料看来是被胶囊伴护至洗涤水的表面，为所用的香料原料提供了最大的功效。胶囊包封的香料与指定的脂肪酶联合使用也为这些尤其对脂肪酶敏感的香料原料提供了一定程度的保护。
优选地，存在于胶囊包封香料颗粒中的香料油包含一种或多种香料成分，所述香料成分的特征在于其沸点(B.P.)和其辛醇/水分配系数(P)。香料成分的辛醇/水分配系数是它在辛醇和水中的平衡浓度之间的比率。本发明优选的香料成分在约0.10MPa(760mmHg)的正常标准压力下测定时具有约260℃或更低的B.P.，优选小于约255℃，更优选小于约250 ℃，并且具有约1,000或更高的辛醇/水分配系数P。由于本发明优选的香料成分的分配系数具有很高的值，因此更方便地以它们以10为底的对数logP的形式给出。因此，本发明优选的香料成分具有至少3，优选大于3.1，甚至更优选大于3.2的logP。
许多香料成分的沸点在例如，1969年由Steffen Arctander出版的“Perfume and Flavor Chemicals(Aroma Chemicals)，”中给出，引入本发明以供参考。
许多香料成分的logP已经被报导；例如，购自Daylight ChemicalInformation Systems，Inc.(Daylight CIS)，Irvine，California的Pomona92数据库就包含许多香料成分的logP以及对原始文献的引用。然而，最方便地是由同样购自Daylight CIS的“CLOGP”程序计算logP值。当在Pomona92数据库中可得到实验的logP值时，该程序也可列出这些值。“计算的logP”(ClogP)由Hansch和Leo的分段方法测定(参考A.Leo，在Comprehensive Medicinal Chemistry，第4卷，C.Hansch，P.G.Sammens，J.B.Taylor和C.A.Ramsden，Eds.，第295页，Pergamon Press，1990年，引入本发明以供参考)。分段方法基于各香料成分的化学结构，并且考虑到原子的数目和类别、原子连通性和化学键接。对这个物理化学性质最可靠并且最广泛使用的估计ClogP值，优选地代替实验的logP值用在可用于本发明的香料成分的选择中。
因此，当在洗涤剂组合物中使用由具有约260℃或更低的B.P.和约3或更高的ClogP或实验的logP的成分组成的香料组合物时，在使用产品时，香味很充分且很易被察觉。表1给出可用于本发明洗涤剂组合物的优选香料成分的一些非限制性实施例。用于胶囊包封的尤其优选的香料油包括一种成分或超过一种成分的混合物，所述成分选自辛醛、壬醛、癸醛、十二烷基醛(十二烷醛或月桂醛)、二苯醚、α-紫罗兰酮、铃兰醛和α-异“γ”甲基紫罗兰酮。人们发现这些成分对于掩盖由脂肪酸气味所产生的恶臭尤其有用。这些尤其优选的香料油可单独地胶囊包封，或作为与其它优选的(即下表1中列出的)或尤其优选的香料油的混合物的一部分胶囊包封，或作为与其它香料油的混合物的一部分胶囊包封。
表1
优选香料成分的实施例
| 香料成分 | 大约BP(℃) | 大约ClogP |
| 异罗勒烯庚酸烯丙酯大茴香脑丁酸苄酯莰烯香芹酚β-石竹烯顺式-3-己烯基巴豆酸酯柠檬醛(橙花醛)香茅醇香茅醇乙酸酯香茅醇异丁酸酯香茅基腈香茅醇丙酸酯乙酸环己基乙酯癸醛二氢月桂烯醇乙酸二氢月桂烯酯二甲基辛醇二苯醚十二内酯 | 192210236240159238256101228225229249225242187209208225213252258 | 4.3623.3013.3143.6984.1923.4016.3333.7003.1203.1933.6704.9373.0944.6283.3214.0083.0303.8793.7374.2404.359 |
| 乙基甲基苯基缩水甘油酸酯乙酸葑基酯γ-甲基紫罗兰酮γ-正-甲基紫罗兰酮γ-壬内酯乙酸香叶酯甲酸香叶酯异丁酸香叶酯香叶基腈异丁酸己烯酯新戊酸己酯巴豆酸己酯α-紫罗兰酮β-紫罗兰酮γ-紫罗兰酮α-鸢尾酮醋酸异冰片酯苯甲酸异丁酯乙酸异壬酯异壬醇异丁基喹啉异薄荷醇对异丙基苯乙醛异蒲勒醇月桂醛(十二烷醛)铃兰醛(p-t-Bucinal)d-柠檬烯乙酸里哪酯乙酸薄荷酯甲基胡椒酚α-异“γ”甲基紫罗兰酮甲基壬基乙醛 | 260220230252243245216245222182224231237239240250227242200194252219243212249258177220227216230232 | 3.1653.4854.0894.3093.1403.7153.2694.3933.1393.1814.3743.8003.3813.9603.7803.8203.4853.0283.9843.0784.1933.0303.2113.3305.0663.8584.2323.5003.2103.0744.2094.846 |
| 甲基辛基乙醛月桂烯橙花醛橙花醇乙酸酯乙酸壬酯壬醛辛醛橙萜烯(d-柠檬烯)对甲基异丙基苯苯基庚醇苯基己醇α-蒎烯β-蒎烯α-萜品烯γ-萜品烯萜品油烯乙酸萜品酯四氢里哪醇四氢月桂烯醇吐纳麝香十一碳烯醛藜芦醚乙酸邻叔丁基环己酯醋酸对叔丁基环己酯 | 228167228231212212223177179261258157166176183184220191208246223206221232 | 4.3174.2723.1203.5554.3743.4793.8454.2324.0683.4783.2994.1224.1824.4124.2324.2323.4753.5173.5176.2474.0533.1404.0594.060 |
在胶囊包封之前，胶囊包封香料颗粒中的香料油可被吸附或被吸附到载体上。合适的载体描述于WO97/11151。尤其优选的载体为沸石。
本文的洗涤剂组合物包含约0.01％至50％的胶囊包封的香料颗粒。更优选地，本文的洗涤剂组合物包含0.05％至8.0％，甚至更优选0.5％至3.0％的香料颗粒。最优选地，本文的洗涤剂组合物包含0.05％至1.0％的胶囊包封的香料颗粒。胶囊包封的香料颗粒优选具有1微米至1000微米，更优选50微米至500微米的尺寸。
香料油和/或香料组合物通常存在于本发明洗涤剂组合物中的量为0.001％至约5％，优选0.01％至5％，更通常0.05％至3％。当存在于本发明的洗涤剂组合物中时，优选的香料成分可包含100％的香料油，但是更通常的是在其它香料成分基础上使用。可存在超过一种优选香料成分的混合物，例如至少2种，或甚至至少5种或6种或7种不同的优选香料成分。此外，胶囊包封的香料颗粒可包含至少1％或5％或10％重量，或甚至至少20％、30％、40％、50％、60％、70％、80％或90％重量的此类优选香料成分。
衍生自天然或合成来源的大多数常用香料成分由许多组分组成。例如，橙萜烯包含约90％至约95％的d-柠檬烯，但是也包含许多其它微量成分。当每种这样的物质用在本发明香料油的制剂中时，为了限定本发明，它被算作一种成分。
除了胶囊包封的香料油之外，洗涤剂组合物还可包含附加的香料油，它们形成洗涤剂组合物中总香料组合物的一部分。可通过任何其它递送方法将附加的香料油掺入到洗涤剂组合物中。例如，在混合以形成成品洗涤剂组合物之前，仅将附加的香料油喷到成品洗涤剂组合物上或喷到洗涤剂组合物的一种组分上。
胶囊包封的香料颗粒也可包括含酯的香料油，所述酯衍生自含有1至7个碳原子的脂肪酸。当洗涤剂组合物也包含附加的香料油时，优选至少60％重量，或至少80％或90％或基本上全部衍生自含有1至7个碳原子的脂肪酸的酯，将存在于胶囊包封的香料颗粒中。
在本发明的另一个方面，洗涤剂组合物中胶囊包封的香料油和/或香料组合物，包含至少10％、20％、30％、40％、50％、60％、70％、80％或甚至90％的一种或多种香料成分，所述香料成分具有大于0但小于或等于5.81E-22g(350道尔顿)，约1.66E-22g(100道尔顿)至约5.81E-22g(350道尔顿)，约2.16E-22g(130道尔顿)至约4.48E-22g(270道尔顿)，或甚至约2.32E-22g(140道尔顿)至约3.82E-22g(230道尔顿)的分子量；至少80％、85％、90％或甚至95％的所述一种或多种香料成分具有至少2.4，约2.75至约8.0，或甚至约2.9至约6.0的cLogP，所述香料组合物包含至少5％、15％、25％、35％、45％、55％、65％、75％、85％或甚至95％的所述一种或多种香料成分，所述香料成分具有在至少2.4，约2.75至约8.0，或甚至约2.9至约6.0范围内的cLogP。在本发明的所述方面，所述一种或多种香料成分可选自Schiff碱、醚、酚、酮、醇、酯、内酯、醛、腈、天然油，或它们的混合物。Schiff碱和腈会是最不优选的。在如上文所述的本发明的某些方面，所述一种或多种香料成分可包括表2的香料成分或它们的混合物，或甚至表2的香料成分1至28或它们的混合物。酮和醛可优选具有低于3.32E-22g(200道尔顿)的分子量。
在本发明的另一个方面，所述香料组合物包含至少10％、20％、30％、40％、50％、60％、70％、80％ 或甚至90％ 的香料成分，所述香料成分选自下表2所列出的成分、以及它们的混合物。
表2
| 化学名称 | CAS | 官能度 | MWt | clogP | |
| 1 | 2-甲氧基萘 | 93-04-9 | 醚 | 158 | 3.24 |
| 2 | 二苯醚 | 101-84-8 | 醚 | 170 | 4.24 |
| 3 | 2-甲氧基-4-丙烯基酚 | 120-11-6 | 酚 | 164 | 4.63 |
| 4 | 2-甲氧基-4-烯丙基酚 | 97-53-0 | 酚 | 164 | 2.40 |
| 5 | 4-戊烯-1-酮，1-(5，5-二甲基-1-环己烯-1-基) | 56973-85-4 | 酮 | 192 | 4.0 |
| 6 | (1α(E)，2β)-1-(2，6，6-三甲基--3-环己烯-1-基)-2-丁烯-1-酮 | 71048-82-3 | 酮 | 192 | 3.62 |
| 7 | 3-丁烯-2-酮，3-甲基-4-(2，6，6-三甲基-2-环己烯-1-基) | 127-51-5 | 酮 | 206 | 4.0 |
| 8 | 2-(2-(4-甲基-3-环己烯-1-基)丙基环戊酮 | 95962-14-4 | 酮 | 220 | 4.44 |
| 9 | 4-[(2，6，6-三甲基-1-环己-2-烯基)]-3-丁烯-2-酮 | 127-41-3 | 酮 | 192 | 3.71 |
| 10 | 1-丁烯-1-醇，2-乙基-4-(2，2，3-三甲基-3-环戊烯-1-基)- | 28219-61-6 | 醇 | 208 | 4.43 |
| 11 | 2-乙基-4-(2，2，3-三甲基-3-环戊烯基-1)-2-丁烯-1-醇 | 28219-61-6 | 醇 | 208 | 4.43 |
| 12 | 环戊烷乙酸，3-氧代-2-戊基-甲基酯 | 24851-98-7 | 酯 | 226 | 2.42 |
| 13 | 2-己基-3-氧代-环戊烷羧酸甲酯 | 37172-53-5 | 酯 | 226 | 3.09 |
| 14 | 三环癸烯基丙酸酯 | 17511-60-3 | 酯 | 206 | 2.89 |
| 15 | 三环癸烯基乙酸酯 | 2500-83-6 | 酯 | 190 | 2.36 |
| 16 | 水杨酸正戊酯 | 2050-08-0 | 酯 | 208 | 4.56 |
| 17 | 苯并吡喃-2-酮或1，2-苯并吡喃酮 | 91-64-5 | 内酯 | 146 | 1.41 |
| 18 | 4-(三环(5，2，1，0)亚癸基-8)正丁醛 | 30168-23-1 | 醛 | 204 | 3.63 |
| 19 | 3-(3-异丙基苯基)正丁醛 | 125109-85-5 | 醛 | 190 | 3.55 |
| 20 | 对叔丁基-α-甲基二氢肉桂醛 | 80-54-6 | 醛 | 204 | 3.86 |
| 21 | α-己基肉桂醛 | 101-86-0 | 醛 | 216 | 4.85 |
| 22 | 正辛醛 | 124-13-0 | 醛 | 128 | 2.95 |
| 23 | 正壬醛 | 124-19-6 | 醛 | 142 | 3.98 |
| 24 | 正癸醛 | 10486-19-8 | 醛 | 156 | 5.60 |
| 25 | 十二烷醛 | 112-54-9 | 醛 | 184 | 5.07 |
| 26 | α-乙烯基-α-甲基苯乙腈 | 97384-48-0 | 腈 | 171 | 2.31 |
| 27 | 2-环亚己基-2-苯乙腈 | 104621-98-0 | 腈 | 197 | 无 |
| 28 | 绿叶刺蕊草 | 无 | 天然油 | 无 | 无 |
| 29 | 萘[2，1-b]呋喃，十二氢-3a，6，6，9a-四甲基- | 3738-00-9 | 醚 | 236 | 5.26 |
| 30 | 环戊酮，2-戊基- | 4819-67-4 | 酮 | 154 | 2.94 |
| 31 | 乙酮，1-(1，2，3，4，5，6，7，8-八氢-2，3，8，8-四甲基-2-萘基)- | 54464-57-2 | 酮 | 234 | 4.84 |
| 32 | 3-甲基-4(5)-环十五烯酮 | 82356-51-2 | 酮 | 236 | 5.60 |
| 33 | 2(3H)-呋喃酮，5-庚基二氢- | 104-67-6 | 内酯 | 184 | 3.83 |
| 34 | 甲基紫罗兰酮(混合物) | 1335-46-2 | 酮 | 206 | 4.23 |
| 35 | 螺[1，3-二氧戊环-2，8′(5′H)-[2H-2，4a]甲基萘]，六氢-1′，1′，5′，5′-四甲基-，[2′S-(2′.α.，4′a.α.，8′a.α.)]- | 154171-77-4 | 酮 | 无 | 5.67 |
| 36 | 十一醛，2-甲基- | 110-41-8 | 醛 | 184 | 4.85 |
| 37 | 10-十一烯醛 | 112-45-8 | 醛 | 168 | 4.05 |
| 38 | 4-甲基-3-癸烯-5-醇 | 81782-77-6 | 醇 | 170 | |
| 39 | 苯甲酸，2-羟基-，环己酯 | 25485-88-5 | 酯 | 220 | 4.48 |
| 40 | 4H-二氢茚-4-酮，1，2，3，5，6，7-六氢-1，1，2，3，3-五甲基- | 33704-61-9 | 酮 | 206 | 3.99 |
| 41 | N-2，4-二甲基-3-环己烯亚甲基氨茴酸甲酯 | 68738-99-8 | 席夫碱 | 无 | 4.78 |
| 42 | 2-丁烯-1-醇，2-乙基-4-(2，2，3-三甲基-3-环戊烯-1-基)- | 28219-61-6 | 醇 | 208 | 4.43 |
| 43 | 乙酸，己基酯 | 142-92-7 | 酯 | 144 | 2.83 |
| 44 | 1，6-辛二烯-3-醇，3，7-二甲基- | 78-70-6 | 醇 | 154 | 2.55 |
| 45 | 环己醇，2-(1，1-二甲基乙基)-，乙酸 | 88-41-5 | 酯 | 198 | 4.06 |
| 酯 | |||||
| 46 | 2-丁酮，4-(4-羟基苯基)- | 5471-51-2 | 酮 | 164 | 1.07 |
| 47 | 乙酮，1-(2，3，4，7，8，8a-六氢-3，6，8，8-四甲基-1H-3a，7-甲酰氧甘菊环-5-基)-，[3R-(3.α.，3a.β.，7.β.，8a.α.)]- | 32388-55-9 | 酮 | 246 | 4.75 |
| 48 | 环十二烷，(乙氧基甲氧基)- | 58567-11-6 | 醚 | 242 | 5.48 |
| 49 | 环己烷，3-乙氧基-1，1，5-三甲基，顺式- | 24691-15-4 | 醚 | 156 | 3.93 |
| 50 | 1，3-苯并间二氧杂环戊烯-5-甲醛 | 120-57-0 | 醚/醛 | 150 | 1.14 |
| 51 | 苯甲酸，2-羟基-，苯基甲基酯 | 118-58-1 | 酯 | 228 | 4.22 |
| 52 | 2-环戊烯-1-酮，2-甲基-3-(2-戊烯基)- | 11050-62-7 | 酮 | 164 | 2.64 |
| 53 | 氧杂环十六烯-2-酮 | 34902-57-3 | 内酯 | 238 | 5.40 |
| 54 | 4-环十五烯-1-酮，(Z)- | 0014595-54-1 | 酮 | 222 | 无 |
| 55 | 苯甲酸，2-[(7-羟基-3，7-二甲基亚辛基)氨基]-，甲基 | 89-43-0 | 席夫碱 | 305 | 4.17 |
| 56 | 4，7-甲撑-3aH-茚-3a-羧酸，八氢-，乙酯，(3a.α.，4.β.，7.β.，7a.α.)- | 80623-07-0 | 酯 | 209 | 3.37 |
| 57 | 苯甲酸，2-羟基-，3-己烯酯，(Z)- | 65405-77-8 | 酯 | 220 | 4.61 |
| 58 | 苯甲酸，2-氨基-，甲酯 | 134-20-3 | 酯 | 151 | 2.02 |
| 59 | 苯甲酸，2-羟基-，己基酯 | 6259-76-3 | 酯 | 222 | 5.09 |
| 60 | 碳酸，4-环辛-1-烯基甲基酯 | 87731-18-8 | 酯 | 184 | 2.77 |
| 61 | 5-环十六烯-1-酮 | 37609-25-9 | 酮 | 236 | 5.97 |
| 62 | 环己烷丙酸，2-丙烯基酯 | 705-87-5 | 酯 | 196 | 3.93 |
| 63 | 戊酸，2-甲基-，乙酯，(S)- | 28959-02-6 | 酯 | 144 | 2.61 |
| 64 | 3-丁烯-2-酮，4-(2，6，6-三甲基-1-环己-1-烯基)-，(E)- | 79-77-6 | 酮 | 192 | 3.77 |
| 65 | 1，3-二氧戊环，2，4-二甲基-2-(5，6，7，8-四氢-5，5，8，8-四甲基-2-萘基)-，顺式 | 131812-51-6 | 醚 | 288 | 6.27 |
| 66 | 2，6-辛二烯腈，3，7-二甲基- | 5146-66-7 | 腈 | 227 | 3.25 |
| 67 | 2，6-壬二烯腈，3，7-二甲基- | 61792-11-8 | 腈 | 163 | 3.78 |
| 68 | 3-环己烯-1-羧基醛，二甲基- | 27939-60-2 | 醛 | 138 | 2.53 |
| 69 | 氧杂环十六烷基-2-酮 | 106-02-5 | 内酯 | 240 | 6.29 |
| 70 | 甲基-2-甲基-3-(4-叔丁基苯基)亚丙基氨基苯甲酸酯 | 91-51-0 | 席夫碱 | 337 | 6.31 |
| 71 | 乙酸，(3-甲基丁氧基)-，2-丙烯基酯 | 67634-00-8 | 酯 | 186 | 2.38 |
| 72 | 9-十一烯醛，2，6，10-三甲基- | 141-13-9 | 醛 | 210 | 5.16 |
| 73 | 环戊酮，3-甲基-2-戊基- | 13074-63-0 | 酮 | 168 | 3.46 |
在前述任一方面，如果香料油或组合物包含酯香料成分，当所述香料油或组合物包含酯香料组分时，所述酯香料可具有一个或多个以下特征：在α、β或γ位置中的至少一处具有分支或下垂环；在α或β位置中的至少一处具有分支或下垂环；或在α位置有至少一个叔碳原子。不受理论的限制，据信当所述香料酯与可水解酯键的酶，例如分类在EC 3.1.1中的酶(如脂肪酶)同时存在时，前述香料酯的特征导致香料酯的稳定性增强，因此导致香料组合物的稳定性增强。
在本发明前述任一个方面，所述香料油或组合物典型地包含不超过约5％，或甚至没有一种香料组分选自乙酸，苯基甲基；苯乙醇；丁酸，2-甲基-，乙酯；4H-吡喃-4-酮，2-乙基-3-羟基-；苯甲醛，4-羟基-3-甲氧基-；苯甲醛，3-乙氧基-4-羟基-；3-己烯-1-醇，乙酸酯，(Z)-；丁酸，2-甲基-，1-；甲基乙基酯；3-癸酮，1-羟基-；2-庚酮；苯甲醛；丙烷腈，3-(3-己烯氧基)-，(Z)-；2-丁酮，4-苯基-；2-己烯-1-醇；2(3H)-呋喃酮，5-丁基二氢-。
制造香料组合物的方法
本发明的香料组合物可通过混合典型为液体的香料原料来制造。某些香料原料为固体物质，因此可能需要温和加热来同香料的其余部分混匀。香料共混物也可包含显著比例的稀释剂(例如双丙甘醇)、抗氧化剂或增溶的物质。为了将香料分散在显著亲水的基质如含水液体清洁剂中，当表面活性剂含量低时，增溶剂会是尤其有利的。
香料递送方法
香料组合物的前述任一个方面可同其它原料联合来生产以下递送体系中的任何一种来将附加的香料油递送入洗涤剂组合物：喷上香料油、直接喷到洗涤剂组合物或其组分上、淀粉胶囊包封递送体系、多孔载体材料递送体系、涂敷的多孔载体材料递送体系、微胶囊包封递送体系。优选地，本发明的洗涤剂组合物将包括胶囊包封和喷上的香料。生产前述递送体系的合适方法可见于以下美国专利6,458,754、5,656,584、6,172,037、5,955,419和5,691,383以及WIPO公布WO94/28017、WO 98/41607、WO 98/52527中的一个或多个。此类递送体系可在消费品中单独使用、同其它体系联合使用，或甚至同本发明喷射的纯香料组合物或混合的香料组合物联合使用。
除了脂肪酶和胶囊包封的香料颗粒之外，本发明的洗涤剂组合物也将包含一种或多种常规的洗涤剂成分和/或洗涤剂辅助成分。
任选去污助剂
本发明的洗涤剂组合物可以为任何方便的形式，如粉末状或颗粒状固体、条、片剂或非水的液体，包括凝胶和糊剂形式。其它形式的清洁组合物包括其它公共机构的和/或家庭的清洁组合物，如液体或固体清洁和消毒剂，包括抗菌车用清洁剂或地毯清洗剂、假牙清洁剂、硬质表面清洁剂，例如用于厨房和/或浴室用途的任选用于清洁金属的清洁剂、洗发剂、沐浴凝胶、沐浴泡沫，以及诸如漂白添加剂和“去污棒”或预处理类型的清洁助剂。当以颗粒状存在时，本发明的洗涤剂组合物优选为具有350至1200g/L，更优选450至1000g/L或甚至500至900g/L的总堆积体积密度的那些。优选地，颗粒状洗涤剂组合物的洗涤剂颗粒具有200μm至2000μm，优选350μm至600μm大小的平均粒度。
通常，本发明的洗涤剂组合物将同其它洗涤剂颗粒一起混合，其它洗涤剂颗粒包括附聚物、喷雾干燥的粉末和/或诸如漂白剂、酶等等干燥添加的物质的组合。
作为优选的实施方案，常规的洗涤剂成分选自典型的洗涤剂组合物组分，如去污表面活性剂和去污助洗剂。任选地，洗涤剂成分可包括一种或多种其它去污助剂，或其它用于帮助或提高清洁性能、处理待清洁的基质或改变洗涤剂组合物美观的物质。洗涤剂组合物的常见去污助剂包括Baskerville等人的美国专利3,936,537和1997年9月24日公布的Trinh等人的英国专利申请9705617.0中所阐述的成分。此类助剂以它们常规的领域-确定的用量包括在洗涤剂组合物中，通常为0％至约80％的洗涤剂成分，优选约0.5％至约20％，并且可包括彩色斑点、增泡剂、抑泡剂、防锈和/或防腐蚀剂、污垢-悬浮剂、去污剂、染料、填充剂、荧光增白剂、杀菌剂、碱度来源、水溶助长剂、抗氧化剂、酶、酶稳定剂、溶剂、增溶剂、螯合剂、粘土污垢移除/抗-再沉淀剂、聚合分散剂、加工助剂、织物软化组分、静电控制剂、漂白剂、漂白活化剂、漂白稳定剂等等。
如上所述，包含本发明颗粒的洗涤剂组合物将包含至少一些常用的洗涤剂助剂物质，如附聚物、挤出物、组成与本发明那些喷雾干燥颗粒不同的其它喷雾干燥颗粒、或干燥添加物质。按照惯例，将表面活性剂连同固体物质(通常为助洗剂)一起掺入到附聚物、挤出物或喷雾干燥颗粒中，并且这些可与本发明的喷雾干燥颗粒混合。然而，如上所述，可用本发明的颗粒替换一些或全部固体物质。
洗涤剂助剂物质典型选自由下列物质组成的组：去污表面活性剂、助洗剂、聚合共助洗剂、漂白剂、螯合剂、酶、抗再沉淀聚合物、去污聚合物、聚合污垢分散和/或污垢悬浮剂、染料转移抑制剂、织物完整剂、抑泡剂、织物软化剂、絮凝剂、香料、增白剂、光漂白剂、以及它们的组合。
这些附加组分的精确性质及其掺入含量将取决于组合物或组分的物理形式以及其应用的洗涤操作的精确性质。
一种高度优选的助剂组分是表面活性剂。优选地，洗涤剂组合物包含一种或多种表面活性剂。典型地，洗涤剂组合物包含(按所述组合物的重量计)0％至50％，优选5％，更优选10％或甚至15％重量至40％或至30％或至20％的一种或多种表面活性剂。优选的表面活性剂是阴离子表面活性剂、非离子表面活性剂、阳离子表面活性剂、两性离子表面活性剂、两性表面活性剂、阳离子表面活性剂、以及它们的混合物。
优选的阴离子表面活性剂包括选自碳酸根、磷酸根、硫酸根、磺酸根以及它们的混合的一个或多个部分。优选的阴离子表面活性剂是C8-18烷基硫酸盐和C8-18烷基磺酸盐。单独或以混合物形式掺入到本发明的组合物中的合适阴离子表面活性剂也是C8-18烷基硫酸盐和/或C8-18烷基磺酸盐，任选地，每摩尔C8-18烷基硫酸盐和/或C8-18烷基磺酸盐与1至9摩尔C1-4烯化氧缩合。C8-18烷基硫酸盐和/或C8-18烷基磺酸盐的烷基链可为直链或支链的，优选的支链烷基链包括一个或多个为C1-6烷基的支链部分。其它优选的阴离子表面活性剂是C8-18烷基苯硫酸盐和/或C8-18烷基苯磺酸盐。C8-18烷基苯硫酸盐和/或C8-18烷基苯磺酸盐的烷基链可为直链或支链的，优选的支链烷基链包括一个或多个为C1-6烷基的支链部分。
其它优选的阴离子表面活性剂选自：C8-18链烯基硫酸盐、C8-18链烯基磺酸盐、C8-18链烯基苯硫酸盐、C8-18链烯基苯磺酸盐、C8-18烷基二甲基苯硫酸盐、C8-18烷基二甲基苯磺酸盐、脂肪酸酯磺酸盐、二烷基磺基琥珀酸盐、以及它们的组合。阴离子表面活性剂可以盐的形式存在。例如，阴离子表面活性剂可以是一种或多种化合物的碱金属盐，所述化合物选自：C8-18烷基硫酸盐、C8-18烷基磺酸盐、C8-18烷基苯硫酸盐、C8-C18烷基苯磺酸盐、以及它们的组合。优选的碱金属是钠、钾、以及它们的混合物。典型地，洗涤剂组合物包含10％至30％重量的阴离子表面活性剂。
优选的非离子表面活性剂选自：每摩尔C8-18醇与1至9摩尔C1-C4烯化氧缩合的C8-18醇的缩合产物、C8-18烷基N-C1-4烷基葡糖酰胺、C8-18酰氨基C1-4二甲基胺、C8-18烷基多苷、甘油单醚、聚羟基酰胺、以及它们的组合。典型地，本发明的洗涤剂组合物包含0％至15％，优选2％至10％重量的非离子表面活性剂。
优选的阳离子表面活性剂为季铵化合物。优选的季铵化合物包括长烃链和短烃链的混合物，典型地为烷基和/或羟烷基和/或烷氧基化烷基链。典型地，长烃链是C8-18烷基链和/或C8-18羟烷基链和/或C8-18烷氧基化烷基链。典型地，短烃链是C1-4烷基链和/或C1-4羟烷基链和/或C1-4烷氧基化烷基链。典型地，洗涤剂组合物包含(按所述组合物的重量计)0％至20％的阳离子表面活性剂。
优选的两性离子表面活性剂包含一个或多个季铵化的氮原子和选自以下离子的一个或多个部分：碳酸根、磷酸根、硫酸根、磺酸根、以及它们的组合。优选的两性离子表面活性剂是烷基甜菜碱。其它优选的两性离子表面活性剂是烷基胺氧化物。还可包括正负离子表面活性剂，其是包含阳离子表面活性剂和阴离子表面活性剂的配合物。典型地，在配合物中阳离子表面活性剂与阴离子表面活性剂的摩尔比大于1∶1，因此配合物具有净正电荷。
另一种优选的助剂组分是助洗剂。优选地，洗涤剂组合物包含(按所述组合物的重量计并且在无水的基础上)20％至50％的助洗剂。优选的助洗剂选自：无机磷酸盐及其盐，优选正磷酸盐、焦磷酸盐、三聚磷酸盐、它们的碱金属盐、以及它们的组合；多元羧酸及其盐，优选柠檬酸、它们的碱金属盐、以及它们的组合；硅铝酸盐、它们的盐、以及它们的组合，优选无定形硅铝酸盐、结晶硅铝酸盐、混合的无定形/结晶硅铝酸盐、它们的碱金属盐、以及它们的组合，最优选沸石A、沸石P、沸石MAP、它们的盐、以及它们的组合；硅酸盐，如层状硅酸盐、它们的盐、以及它们的组合，优选层状硅酸钠；以及它们的组合。
一种优选的助剂组分是漂白剂。优选地，洗涤剂组合物包含一种或多种漂白剂。典型地，组合物包含(按所述组合物的重量计)1％至50％的一种或多种漂白剂。优选的漂白剂选自过氧化物源、过酸源、漂白增强剂、漂白催化剂、光漂白剂、以及它们的组合。优选的过氧化物源选自：一水合过硼酸盐、四水合过硼酸盐、过碳酸盐、它们的盐、以及它们的组合。优选的过酸源选自：典型具有过氧化物源的漂白活化剂，如过硼酸盐或过碳酸盐、预形成过酸、以及它们的组合。优选的漂白活化剂选自：羟苯磺酸盐漂白活化剂、内酰胺漂白活化剂、酰亚胺漂白活化剂、以及它们的组合。优选的过酸源是四乙酰基乙二胺(TAED)和诸如过碳酸盐的过氧化物源。优选的羟苯磺酸盐漂白活化剂选自：壬酰基羟苯磺酸盐、6-壬酰氨基己酰羟苯磺酸盐、它们的盐、以及它们的组合。优选的内酰胺漂白活化剂是酰基己内酰胺和/或酰基戊内酰胺。优选的酰亚胺漂白活化剂是N-壬酰-N-甲基乙酰胺。
优选的预形成的过酸选自N，N-邻苯二甲酰氨基过氧己酸、壬基酰氨基过氧己二酸、它们的盐、以及它们的组合。优选地，该STW组合物包含一种或多种过氧化物源和一种或多种过酸源。优选的漂白催化剂包含一种或多种过渡金属离子。其它优选的漂白剂是二酰基过氧化物。优选的漂白增强剂选自：两性离子亚胺、阴离子亚胺多离子、季过氧亚胺盐、以及它们的组合。高度优选的漂白增强剂选自：芳香亚胺 两性离子、芳香亚胺 聚离子、以及它们的组合。合适的漂白增强剂描述于US360568、US5360569和US5370826。
一种优选的助剂组分是抗再沉淀剂。优选地，洗涤剂组合物包含一种或多种抗再沉淀剂。优选的抗再沉淀剂是纤维质的聚合物组分，最优选羧甲基纤维素。
一种优选的助剂组分是螯合剂。优选地，洗涤剂组合物包含一种或多种螯合剂。优选地，洗涤剂组合物包含(按所述组合物的重量计)0.01％至10％的螯合剂。优选的螯合剂选自：羟乙烷-二亚甲基-膦酸、乙二胺四(亚甲基膦)酸、二亚乙基三胺五乙酸盐、1，2-乙二胺四乙酸盐、二亚乙基三胺五(甲基磷)酸、乙二胺二琥珀酸、以及它们的组合。
一种优选的助剂组分是染料转移抑制剂。优选地，洗涤剂组合物包含一种或多种染料转移抑制剂。典型地，染料转移抑制剂是聚合物组分，该组分捕获染料分子并且通过将其悬浮在洗涤液体中来保持住所述染料分子。优选的染料转移抑制剂选自：聚乙烯吡咯烷酮、聚乙烯吡啶-N-氧化物、聚乙烯吡咯烷酮-聚乙烯咪唑共聚物、以及它们的组合。
一种优选的助剂组分包括其它酶。优选地，洗涤剂组合物包含一种或多种附加的酶。优选的酶选自：淀粉酶、阿拉伯糖酶、糖酶、纤维素酶、软骨素酶、角质酶、葡聚糖酶、酯酶、β-葡聚糖酶、葡萄糖淀粉酶、透明质酸酶、角质素酶、漆酶、木素酶、脂氧合酶、malanases、甘露聚糖酶、氧化酶、果胶酶、戊聚糖酶、过氧化物酶、酚氧化酶、磷脂酶、蛋白酶、支链淀粉酶、还原酶、鞣酸酶、转移酶、木聚糖酶、木葡聚糖酶、以及它们的组合。优选的附加酶选自：淀粉酶、糖酶、纤维素酶、蛋白酶、以及它们的组合。
一种优选的助剂组分是织物完整剂。优选地，洗涤剂组合物包含一种或多种织物完整剂。典型地，织物完整剂是聚合物组分，该组分在洗衣过程中沉积在织物表面上并防止织物损坏。优选的织物完整剂是疏水改性的纤维素。这些疏水改性的纤维素能够减少织物磨损，增强纤维与纤维的相互作用，并且减少织物的染料流失。优选的疏水改性纤维素描述于WO99/14245。其它优选的织物完整剂是聚合物组分和/或低聚物组分，它们是可获得的，优选通过包括咪唑与表氯醇缩合步骤的过程获得。
一种优选的助剂组分是盐。优选地，洗涤剂组合物包含一种或多种盐。盐可充当碱性剂、缓冲剂、助洗剂、辅助洗剂、结垢抑制剂、填充剂、pH调节剂、稳定剂、以及它们的组合。典型地，洗涤剂组合物包含(按所述组合物的重量计)5％至60％的盐。优选的盐是铝酸盐、碳酸盐、氯化物、碳酸氢盐、硝酸盐、磷酸盐、硅酸盐、硫酸盐、以及它们的组合的碱金属盐。其它优选的盐是铝酸盐、碳酸盐、氯化物、碳酸氢盐、硝酸盐、磷酸盐、硅酸盐、硫酸盐、以及它们的组合的碱土金属盐。特别优选的盐是硫酸钠、碳酸钠、碳酸氢钠、硅酸钠、硫酸钠、以及它们的组合。任选地，所述碱金属盐和/或碱土金属盐可以是无水的。
一种优选的助剂组分是去污剂。优选地，洗涤剂组合物包含一种或多种去污剂。典型地，去污剂是聚合物，其修饰织物表面并且防止污垢再沉积在所述织物上。优选的去污剂是共聚物，优选包括一个或多个对苯二酸酯单元的嵌段共聚物。优选的去污剂是由二甲基对苯二酸酯、1，2-丙二醇和甲基封端的聚乙二醇合成的共聚物。其它优选的去污剂是阴离子封端的聚酯。
一种优选的助剂组分是污垢悬浮剂。优选地，洗涤剂组合物包含一种或多种污垢悬浮剂。优选的污垢悬浮剂是聚合的聚羧酸酯。特别优选的是衍生自丙烯酸的聚合物、衍生自马来酸的聚合物和衍生自马来酸和丙烯酸的共聚物。除了它们的污垢悬浮性能之外，聚合的聚羧酸酯还是衣物洗涤剂的有益辅助洗剂。其它优选的污垢悬浮剂是烷氧基化聚亚烷基亚胺。特别优选的烷氧基化聚亚烷基亚胺是乙氧基化聚乙烯亚胺，或乙氧基化-丙氧基化聚乙烯亚胺。其它优选的污垢悬浮剂可用下式表示：
二((C2H5O)(C2H4O)n(CH3)-N+-CxH2x-N+-(CH3)-二((C2H4O)n(C2H5O))，
其中，n＝10至50，并且x＝1至20。任选地，由上式表示的污垢悬浮剂可被硫酸化和/或磺化。
软化体系
本发明的洗涤剂组合物可包含用于通过洗涤软化的软化剂(如粘土)，还可任选含有絮凝剂和酶。
合适洗涤剂组分的进一步更具体的描述可见于WO97/11151。
洗涤方法
本发明也包括洗涤纺织品的方法，所述方法包括清洁、处理和/或掩盖某个位置例如表面或织物的气味。此方法包括使该位置(如纺织品)同包含本发明洗涤剂组合物的水溶液接触。本发明在低水温(如低于30℃或低于25℃或20℃)时将尤其有益。典型地，含水的洗涤液体将包含至少100ppm，或至少500ppm的洗涤剂组合物。
实施例1：香料组合物
| 通用名称 | CAS | 组 | |||
| 1 | 2 | 3 | 4 | ||
| Yara Yara | 93-04-9 | 5 | |||
| 二苯醚 | 101-84-8 | 2 | 7 | 5 | |
| 异丁子香酚 | 120-11-6 | 6 | |||
| 丁子香酚 | 97-53-0 | 4 | 5 | ||
| Dynascone | 56973-85-4 | 1 | 1.5 | ||
| δ-二氢大马酮 | 71048-82-3 | 2 | 4 | ||
| γ-甲基紫罗兰酮 | 127-51-5 | 20 | 5 | ||
| 仙酒酮 | 95962-14-4 | 20 | |||
| α-紫罗兰酮 | 127-41-3 | 4 | |||
| 大唐檀香 | 28219-61-6 | 8 | |||
| Levosandol | 28219-61-6 | 8 | |||
| Hedione | 24851-98-7 | 25 | 40 | ||
| 二氢IsoJasmonate | 37172-53-5 | 10 | 12 | 5 | |
| Frutene | 17511-60-3 | 25 | |||
| Flor乙酸酯 | 2500-83-6 | 25 | |||
| 水杨酸戊酯 | 2050-08-0 | 20 | |||
| 香豆素 | 91-64-5 | 4 | |||
| 4-(三环-[5.2.1.0]-癸基-8)丁醛 | 30168-23-1 | 1 | |||
| Florhydral | 125109-85-5 | 2 | |||
| 铃兰醛 | 80-54-6 | 20 | 20 | ||
| 己基肉桂醛 | 101-86-0 | 40 | |||
| 醛C10 | 10486-19-8 | 5 | |||
| 月桂醛 | 112-54-9 | 1.5 | |||
| Peonile | 104621-98-0 | 15 | 12 | ||
| 绿叶刺蕊草 | 10 | ||||
| 余量 | 100 | 100 | 100 | 100 | |
实施例2：用来自实施例1的组合物制成的香料。
| 香料实施例 | |||||
| 通用名称 | CAS | A | B | C | D |
| 组合物1 | 无 | 61 | |||
| 组合物2 | 无 | 45 | |||
| 组合物3 | 无 | 26 | |||
| 组合物4 | 无 | 10 | |||
| 降龙涎醚 | 3738-00-9 | 05 | |||
| 戈基环酮 | 4819-67-4 | 2 | |||
| δ-麝香烯酮 | 82356-51-2 | 1 | |||
| 十一烷酸内酯 | 104-67-6 | 1 | |||
| 醛MNA | 110-41-8 | 2 | |||
| 4-甲基-3-癸烯-5-醇 | 81782-77-6 | 2 | |||
| 水杨酸环己酯 | 25485-88-5 | 3 | |||
| Cashmeran | 33704-61-9 | 1 | |||
| Agrumea | 68738-99-8 | 3 | |||
| 乙酸己酯 | 142-92-7 | 5 | |||
| 乙酸邻叔丁基环己酯 | 88-41-5 | 10 | |||
| 甲基柏木酮 | 32388-55-9 | 2 | |||
| 洋茉莉醛 | 120-57-0 | 1 | |||
| 水杨酸苄酯 | 118-58-1 | 4 | |||
| 异茉莉酮 | 11050-62-7 | 1 | |||
| Habanolide | 34902-57-3 | 5 | 5 | ||
| 橙花素 | 89-43-0 | 1 | |||
| 水杨酸顺式-3-己烯酯 | 65405-77-8 | 3 | |||
| 氨茴酸甲酯 | 134-20-3 | 1 | |||
| 水杨酸己酯 | 6259-76-3 | 4 | |||
| 2-甲基戊酸乙酯 | 28959-02-6 | 1 | |||
| 香叶基腈 | 5146-66-7 | 2 | |||
| 女贞醛 | 27939-60-2 | 1 | 2 | ||
| 烯丙基戊基乙醇酸酯 | 67634-00-8 | 1 | |||
| 阿道克醛 | 141-13-9 | 05 | |||
| Jasmylone | 13074-63-0 | 1 | |||
| 乙酸苄酯 | 140-11-4 | 10 | 58 | ||
| 苯乙醇 | 60-12-8 | 34 | |||
| 香草醛 | 121-33-5 | 1 | |||
| 乙基香草醛 | 121-32-4 | 05 | |||
| 乙酸顺式-3-己烯酯 | 3681-71-8 | 1 | |||
| 肉桂腈 | 1885-38-7 | 1 | |||
| 苄基丙酮 | 2550-26-7 | 20 | 20 | ||
| βγ己烯醇 | 2305-21-7 | 1 | 2 | 1 | |
| γ辛内酯 | 104-50-7 | 0.5 | 1 | ||
| D-柠檬烯 | 138-86-3 | 15 | 26 | ||
| 总计 | 100 | 100 | 100 | 100 |
在以下的胶囊包封和洗涤剂组合物中，香料组分为依照本发明和/或上述实施例1和2的香料。
改性淀粉胶囊包封的香料颗粒的制造
实施例3
1.将225g的CAPSUL改性淀粉(National Starch & Chemical)于24℃加到450g水中。
2.以62.8rad/s(600RPM)(涡轮叶轮直径5.08cm(2英寸))的速度搅拌混合物20分钟。
3.邻近淀粉溶液的涡旋加入75g香料油。
4.再搅拌形成的乳液20分钟(以62.8rad/s(600RPM)速度)。
5.在获得小于15微米的香料液滴尺寸之后，用泵将乳液抽到喷雾干燥塔，并且通过旋流片喷成雾状，其中有用于干燥的顺流空气流。进口空气温度设定在205℃至210℃，出口空气温度稳定在98℃至103℃。
6.在烘干机出口收集淀粉胶囊包封香料油的干燥颗粒。
完成的香料颗粒的分析(所有％均基于重量)：
全部香料油 24.56％
胶囊包封的油/游离的或表面油 24.46％/0.10％
淀粉 72.57％
水分 2.87％
粒径分布
＜50微米 16％
50-500微米 83％
＞500微米 1％
实施例4
在合适的容器中，将500g的HiCap 100改性淀粉(由NationalStarch & Chemical供应)溶入1000g去离子水中。一旦获得均一化溶液，就将40g无水柠檬酸加入淀粉溶液中。搅拌混合物10分钟以溶解柠檬酸。此时，将600g香料加入混合物中。然后用高剪切搅拌器(ARD-Barico)再搅拌乳液10分钟。
然后在由Niro A/S制造的Production Minor直流喷雾器烘干机中将混合物喷雾干燥。使用同样来自Niro A/S的FS1型旋转离心喷雾盘。空气入口温度为200℃，出口温度为90℃。盘速度设定在2984.5rad/s(28,500rpm)。在喷雾干燥乳液之前，通过喷水30分钟将塔稳定在这些条件下。干燥的颗粒收集在旋风集尘器中。
包含实施例3和4的胶囊包封香料的洗涤剂组合物例示于下表3中：
表3
| 成分 | A | B | C | D | E |
| 直链C11-13烷基苯磺酸钠 | 11％ | 12％ | 10％ | 18％ | 15％ |
| R2N+(CH3)2(C2H4OH)，其中R2＝C12-14烷基 | 0.6％ | 1％ | 0.6％ | ||
| 中链甲基支化的C12-C14直链烷基硫酸钠 | 1.4％ | 1.2％ | 1％ | ||
| C12-18直链烷基硫酸钠 | 0.7％ | 0.5％ | |||
| C12-18直链烷基乙氧基化物，其中每摩尔烷基醇与平均3至9摩尔环氧乙烷缩合 | 1％ | 4％ | 2％ | 3％ | 1％ |
| 柠檬酸 | 2％ | 1.5％ | 2％ | ||
| 三聚磷酸钠(以无水重量给出) | 25％ | 22％ | |||
| 羧甲基纤维素钠 | 0.2％ | 0.2％ | 0.3％ | ||
| 聚丙烯酸钠聚合物，具有3000至5000的重均分子量 | 2.0％ | 0.5％ | 1％ | 0.7％ | |
| 马来酸/丙烯酸共聚物，具有50,000至90,000的重均分子量，其中马来酸与丙烯酸的比率为1∶3至1∶4(购自BASF的Sokalan CP5) | 2.1％ | 3.5％ | 7％ | 2.0％ | 2.1％ |
| 二亚乙基三胺五醋酸 | 0.2％ | 1.0％ | 0.2％ | 0.3％ | |
| 乙二胺二琥珀酸 | 0.5％ | 0.6％ | 0.5％ | ||
| 蛋白分解酶，具有15mg/g至70mg/g的酶活性 | 0.2％ | 0.2％ | 0.5％ | 0.4％ | 0.3％ |
| 淀粉分解酶，具有25mg/g至50mg/g的酶活性 | 0.2％ | 0.2％ | 0.3％ | 0.4％ | 0.3％ |
| 来自Novozymes的Lipex酶，具有5mg/g至25mg/g的酶活性 | 0.2％ | 0.5％ | 0.1％ | 0.5％ | 0.3％ |
| 无水一水合过硼酸钠 | 20％ | 5％ | 8％ | ||
| 过碳酸钠 | 10％ | 12％ |
| 硫酸镁 | 0.1％ | 0.5％ | |||
| 壬酰基羟苯磺酸盐 | 2％ | 1.2％ | |||
| 四乙酰基乙二胺 | 3％ | 4％ | 2％ | 0.6％ | 0.8％ |
| 增白剂 | 0.1％ | 0.1％ | 0.2％ | 0.1％ | 0.1％ |
| 碳酸钠 | 10％ | 10％ | 10％ | 19％ | 22％ |
| 硫酸钠 | 20％ | 15％ | 5％ | 5％ | 6％ |
| 沸石A | 25％ | 20％ | 20％ | 17％ | 14％ |
| 硅酸钠(2.0R) | 0.2％ | 1％ | 1％ | ||
| 结晶层状硅酸盐 | 3％ | 5％ | 10％ | ||
| 光漂白剂 | 0.002％ | ||||
| 聚环氧乙烷，具有100至10,000的重均分子量 | 2％ | 1％ | |||
| 喷上的香料 | 0.2％ | 0.5％ | 0.25％ | 0.1％ | |
| 来自实施例1或实施例2的淀粉胶囊包封的香料 | 0.4％ | 0.5％ | 1％ | 0.4％ | 1.5％ |
| 硅氧烷基抑泡剂 | 0.05％ | 0.05％ | 0.02％ | ||
| 皂 | 1.2％ | 1.5％ | 1.0％ | ||
| 杂项和水分 | 至100％ | 至100％ | 至100％ | 至100％ | 至100％ |
Claims (10)
1.一种洗涤剂组合物，所述组合物包含：
(1)一种脂肪酶，该脂肪酶为具有下述氨基酸序列的多肽：a)具有与得自Humicola lanuginosa菌株DSM 4109的野生型脂肪酶至少90％的同一性；b)与所述野生型脂肪酶相比，包括在三维结构表面距E1或Q24915埃之内一个电中性或带负电的氨基酸被一个带正电的氨基酸所取代；以及c)在C-末端包括一个附加肽段；和/或(d)在N-末端包括一个附加肽段，和/或(e)符合下列限定条件：i)在所述野生型脂肪酶的E210位含有一个带负电的氨基酸；ii)在对应于所述野生型脂肪酶90-101位的区域含有一个带负电的氨基酸；和iii)在对应于所述野生型脂肪酶的N94位含有一个中性或带负电的氨基酸和/或在对应于所述野生型脂肪酶90-101位的区域具有一个负或中性净电荷；和
(2)一种胶囊包封的香料颗粒，该颗粒包括(a)包含一种或多种水溶性羟基化合物的至少部分水溶性的固体基质，优选淀粉；和(b)被固体基质所胶囊包封的香料油。
2.如权利要求1所述的洗涤剂组合物，其中所述胶囊包封的香料油包含按重量计至少1％，或至少5％或至少10％，或按重量计甚至至少40％的至少一种香料成分，所述香料成分在36KNm-2(760mmHg)具有260℃或更低的沸点，并且具有至少3.0的其辛醇/水系数P的log10计算值(ClogP)。
3.如权利要求1或权利要求2所述的洗涤剂组合物，其中所述胶囊包封的香料油包含衍生自具有1至7个碳原子的脂肪酸的酯。
4.如前述任一项权利要求所述的洗涤剂组合物，其中除了所述胶囊包封的香料油之外，附加的香料油还作为喷射组分存在。
5.如权利要求4所述的洗涤剂组合物，其中所述香料油包含衍生自具有1至7个碳原子的脂肪酸的酯，并且至少90％重量的衍生自具有1至7个碳原子的脂肪酸的酯存在于所述胶囊包封的香料颗粒中。
6.如前述任一项权利要求所述的洗涤剂组合物，其中所述胶囊包封的香料颗粒包含乙酸苄酯和/或乙酸苯乙酯。
7.如前述任一项权利要求所述的洗涤剂组合物，其中所述胶囊包封的香料颗粒中的香料油被吸附或被吸附到载体上，并且香料油和载体均被胶囊包封。
8.如前述任一项权利要求所述的洗涤剂组合物，其中所述胶囊包封香料颗粒中的香料油和所述洗涤剂组合物中的任何任选的附加香料油包含香料组合物，所述香料组合物包含至少1％或至少5％重量或甚至10％的一种或多种香料成分，所述香料成分具有大于0但小于或等于350道尔顿的分子量，至少80％的所述一种或多种香料成分具有至少2.4的cLogP，所述香料组合物包含至少1％或甚至至少5％的具有至少2.4的cLogP的所述一种或多种香料成分。
9.一种洗涤方法，所述方法包括在包含如前述任一项权利要求所述的洗涤剂组合物的水溶液中洗涤纺织品。
10.如权利要求9所述的洗涤方法，其中所述水溶液处于30℃以下的温度。
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| TW282393B (zh) * | 1992-06-01 | 1996-08-01 | Dowelanco Co | |
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| US5516448A (en) * | 1994-09-20 | 1996-05-14 | The Procter & Gamble Company | Process for making a high density detergent composition which includes selected recycle streams for improved agglomerate |
| US5691297A (en) * | 1994-09-20 | 1997-11-25 | The Procter & Gamble Company | Process for making a high density detergent composition by controlling agglomeration within a dispersion index |
| US5534179A (en) * | 1995-02-03 | 1996-07-09 | Procter & Gamble | Detergent compositions comprising multiperacid-forming bleach activators |
| US5574005A (en) * | 1995-03-07 | 1996-11-12 | The Procter & Gamble Company | Process for producing detergent agglomerates from high active surfactant pastes having non-linear viscoelastic properties |
| US5569645A (en) * | 1995-04-24 | 1996-10-29 | The Procter & Gamble Company | Low dosage detergent composition containing optimum proportions of agglomerates and spray dried granules for improved flow properties |
| US5597936A (en) * | 1995-06-16 | 1997-01-28 | The Procter & Gamble Company | Method for manufacturing cobalt catalysts |
| US5565422A (en) * | 1995-06-23 | 1996-10-15 | The Procter & Gamble Company | Process for preparing a free-flowing particulate detergent composition having improved solubility |
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| US5656584A (en) * | 1996-02-06 | 1997-08-12 | The Procter & Gamble Company | Process for producing a particulate laundry additive composition for perfume delivery |
| DE69727557T2 (de) * | 1996-03-22 | 2004-12-23 | The Procter & Gamble Company, Cincinnati | Abgabesystem mit Freisetzungsinhibitor beladenem Zeolith und Verfahren zu seiner Herstellung |
| MA24136A1 (fr) * | 1996-04-16 | 1997-12-31 | Procter & Gamble | Fabrication d'agents de surface . |
| CA2282466C (en) * | 1997-03-07 | 2005-09-20 | The Procter & Gamble Company | Bleach compositions containing metal bleach catalyst, and bleach activators and/or organic percarboxylic acids |
| CN1134443C (zh) * | 1997-03-07 | 2004-01-14 | 普罗格特-甘布尔公司 | 制备交联桥大环化合物的改进方法 |
| US6172037B1 (en) * | 1997-05-21 | 2001-01-09 | Quest International B.V. | Perfume fixatives comprising polyvinylpyrrolidone and hydroxypropyl cellulose |
| AU3247699A (en) * | 1998-02-17 | 1999-09-06 | Novo Nordisk A/S | Lipase variant |
| US6458754B1 (en) * | 1998-04-23 | 2002-10-01 | The Procter & Gamble Company | Encapsulated perfume particles and detergent compositions containing said particles |
| EP0965326B1 (en) * | 1998-06-15 | 2007-07-25 | The Procter & Gamble Company | Perfume compositions |
| MXPA01009700A (es) * | 1999-03-31 | 2002-05-14 | Novo Nordisk As | Variante de lipasa. |
| US6833346B1 (en) * | 1999-06-21 | 2004-12-21 | The Procter & Gamble Company | Process for making detergent particulates |
| US6790814B1 (en) * | 1999-12-03 | 2004-09-14 | Procter & Gamble Company | Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes |
| EP1111034A1 (en) * | 1999-12-22 | 2001-06-27 | The Procter & Gamble Company | Laundry and cleaning and/or fabric care compositions |
| DE10012949A1 (de) * | 2000-03-16 | 2001-09-27 | Henkel Kgaa | Kieselsäureester-Mischungen |
| US20020016269A1 (en) * | 2000-07-06 | 2002-02-07 | The Procter & Gamble Co. | Particle perfume delivery system |
| GB0025442D0 (en) * | 2000-10-17 | 2000-11-29 | Unilever Plc | Fabric conditioning compositions |
| JP4287149B2 (ja) * | 2001-02-07 | 2009-07-01 | ノボザイムス アクティーゼルスカブ | リパーゼ変異体 |
| CA2437720C (en) * | 2001-02-14 | 2007-12-18 | The Procter & Gamble Company | Automatic dishwashing compositions comprising diacyl peroxide bleach and blooming perfume |
| DE10140787A1 (de) * | 2001-08-20 | 2003-03-06 | Haarmann & Reimer Gmbh | Depotpräparate |
| GB2382586A (en) * | 2001-12-03 | 2003-06-04 | Procter & Gamble | Fabric treatment compositions |
-
2004
- 2004-11-29 EP EP04257384A patent/EP1661977A1/en not_active Withdrawn
-
2005
- 2005-11-28 DE DE602005026620T patent/DE602005026620D1/de active Active
- 2005-11-28 US US11/287,943 patent/US7569528B2/en active Active
- 2005-11-28 AT AT05025877T patent/ATE500314T1/de not_active IP Right Cessation
- 2005-11-28 JP JP2007543571A patent/JP2008520819A/ja active Pending
- 2005-11-28 AU AU2005309453A patent/AU2005309453A1/en not_active Abandoned
- 2005-11-28 JP JP2007543572A patent/JP2008521974A/ja not_active Withdrawn
- 2005-11-28 MX MX2007006316A patent/MX2007006316A/es unknown
- 2005-11-28 CA CA002586054A patent/CA2586054A1/en not_active Abandoned
- 2005-11-28 US US11/287,659 patent/US20060116304A1/en not_active Abandoned
- 2005-11-28 WO PCT/US2005/042942 patent/WO2006058297A1/en active Application Filing
- 2005-11-28 CN CNA2005800408359A patent/CN101065474A/zh active Pending
- 2005-11-28 AR ARP050104972A patent/AR051972A1/es unknown
- 2005-11-28 MX MX2007006315A patent/MX2007006315A/es active IP Right Grant
- 2005-11-28 WO PCT/US2005/042941 patent/WO2006058296A1/en active Application Filing
- 2005-11-28 CA CA002588677A patent/CA2588677A1/en not_active Abandoned
- 2005-11-28 EP EP05852300A patent/EP1817400A1/en not_active Withdrawn
- 2005-11-28 BR BRPI0516645-4A patent/BRPI0516645A/pt not_active IP Right Cessation
- 2005-11-28 BR BRPI0518692-7A patent/BRPI0518692A2/pt not_active Application Discontinuation
- 2005-11-28 CN CN2005800408382A patent/CN101065473B/zh active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102300550A (zh) * | 2008-12-01 | 2011-12-28 | 宝洁公司 | 香料体系 |
| CN102300550B (zh) * | 2008-12-01 | 2014-04-23 | 宝洁公司 | 香料体系 |
| TWI791474B (zh) * | 2016-11-18 | 2023-02-11 | 日商富士軟片股份有限公司 | 化學液、化學液容器、圖案形成方法以及半導體元件的製造製程用套組 |
| US11747727B2 (en) | 2016-11-18 | 2023-09-05 | Fujifilm Corporation | Chemical liquid, chemical liquid storage body, pattern forming method, and kit |
| CN114867833A (zh) * | 2019-12-19 | 2022-08-05 | 弗门尼舍有限公司 | 洗衣组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2005309453A1 (en) | 2006-06-01 |
| US7569528B2 (en) | 2009-08-04 |
| WO2006058297A1 (en) | 2006-06-01 |
| JP2008520819A (ja) | 2008-06-19 |
| CN101065474A (zh) | 2007-10-31 |
| EP1817400A1 (en) | 2007-08-15 |
| EP1661977A1 (en) | 2006-05-31 |
| BRPI0518692A2 (pt) | 2008-12-02 |
| DE602005026620D1 (de) | 2011-04-14 |
| WO2006058296A1 (en) | 2006-06-01 |
| US20060116304A1 (en) | 2006-06-01 |
| BRPI0516645A (pt) | 2008-09-16 |
| MX2007006316A (es) | 2007-06-19 |
| CN101065473B (zh) | 2012-01-18 |
| AR051972A1 (es) | 2007-02-21 |
| US20060128586A1 (en) | 2006-06-15 |
| ATE500314T1 (de) | 2011-03-15 |
| CA2588677A1 (en) | 2006-06-01 |
| MX2007006315A (es) | 2007-06-19 |
| JP2008521974A (ja) | 2008-06-26 |
| CA2586054A1 (en) | 2006-06-01 |
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